The trans-Bis(p-thioetherphenylacetynyl)bis(phosphine)platinum(II) Ligands: A Step towards Predictability and Crystal Design

Two organometallic ligands L1 ( trans -[ p -MeSC 6 H 4 C≡C-Pt(PR 3 ) 2 -C≡CC 6 H 4 SMe; R = Me]) and L2 (R = Et) react with CuX salts (X = Cl, Br, I) in MeCN to form one-dimensional (1D) or two-dimensional (2D) coordination polymers (CPs). The clusters formed with copper halide can either be step cubane Cu 4 I 4 , rhomboids Cu 2 X 2 , or simply CuI. The formed CPs with L1 , which is less sterically demanding than L2 , exhibit a crystallization solvent molecule (MeCN), whereas those formed with L2 do not incorporate MeCN molecules in the lattice. These CPs were characterized by X-ray crystallography, thermogravimetric analysis, IR, Raman, absorption, and emission spectra as well as photophysical measurements in the presence and absence of crystallization MeCN molecules for those CPs with the solvent in the lattice (i.e., [(Cu 4 I 4 ) L1 ·MeCN] n ( CP1 ), [(Cu 2 Br 2 ) L1 ·2MeCN] n ( CP3 ), and [(Cu 2 Cl 2 ) L1 ·MeCN] n ( CP5 )). The crystallization molecules were removed under vacuum to evaluate the porosity of the materials by Brunauer-Emmett-Teller (N 2 at 77 K). The 2D CP shows a reversible type 1 adsorption isotherm for both CO 2 and N 2 , indicative of microporosity, whereas the 1D CPs do not capture more solvent molecules or CO 2 .